Energy storage technologies with long storage duration are essential to stabilize electricity grids with a high share of intermittent renewable power. In a redox flow battery, the electrochemical conversion unit, where the charging and discharging reaction takes place, is spatially separated from the energy storage medium. In the all-vanadium redox flow battery (VRFB), a sulfuric acid aqueous electrolyte with dissolved vanadium ions is used as the storage medium. Vanadium is present in 4 different oxidation states, the redox couple vanadium(II) and (III) on the negative side of the cell, and vanadium(IV) and (V) on the positive side. This allows the battery to be repeatedly charged and discharged. A separator or membrane is used between the negative and positive electrode, which should selectively conduct the ions of the supporting electrolyte and minimize the passage of vanadium ions. Fluorinated membranes, such as Nafion™, are often used for this key component, but these ionomers were not originally developed for this application and therefore have functional shortcomings. Furthermore, the production and use of fluorinated materials is to be severely restricted or even banned in Europe. Therefore, the development of hydrocarbon-based membranes for the VRFB is of great importance. The study reported here focuses on polybenzimidazole polymers and membranes, which could be a promising materials class for next generation flow batteries.